Copper with other Metal in Bimetallic Catalysis Antonin

Copper with other Metal in Bimetallic Catalysis Antonin Clemenceau Date: 20. 16

Plan • Introduction • Copper and Palladium as bimetallic system • Copper and other metal as bimetallic system • Conclusion 2

Intro: 3

Intro: 4

Intro: 5

Everything started with: The lighthouse of the bimetallic catalysis field 6

Cu/Pd: Wacker reaction Copper used as Oxidant due to the low redox potential of Cu. II/Cu. I (E 0 = 0. 153 V) 7

Cu/Pd: Sonogashira reaction 8

Cu/Pd: Sonogashira reaction Easy insertion of the copper in the alkyne C-H bond 9

Cu/Pd: C-Halkynyl functionalisation Ynone formation: 10

Cu/Pd: C-Halkynyl functionalisation Triazole synthesis 11

Cu/Pd: C-HHeterocycle activation C 2 vs C 5 12

Cu/Pd: C-HHeterocycle activation C 2 vs C 5 13

Cu/Pd: C-HHeterocycle activation C 2 vs C 5 14

Cu/Pd: C-HHeterocycle activation C 2 vs C 3 15

Cu/Pd: Decarboxylative Arylation 16

Cu/Pd: dimer formation 17

Cu/Pd: a-allylation 18

Cu/Pd: Allene formation 19

Other bimetallic sytem Cu/M: - Various possibility with extremely different reactivity - Only some pertinent example will be cover in this part - Cu/Mn, Cu/Fe, Cu/Zr, Cu/Ni, Cu/Ru, Cu/Ir 20

Other bimetallic sytem Cu/Mn: Radical cyclisation from oxidation of acidic C-H bond (developped by B. Snider) Application for total synthesis: 21

Other bimetallic sytem Cu/M Cu/Fe: 22

Other bimetallic sytem Cu/M Cu/Zr: Dynamic kinetic AAA 23

Other bimetallic sytem Cu/M Cu/Ni: Sylation of Csp 2 and Csp 3 24

Other bimetallic sytem Cu/M Cu/Ru: Photoredox - difluroacetylation 25

Other bimetallic sytem Cu/M Cu/Ru: Photoredox 26

Other bimetallic sytem Cu/M Cu/Ir: Photoredox 27

Other bimetallic sytem Cu/M Cu/Ir: Photoredox 28

Conclusion Cu/M: - Explosion of the bimetallic catalysis during the last decades - Copper Cheap metal which offer various possibilities - Photoredox chemistry or asymmetric catalysis can be performed - Be creative with this tool, plenty of other transformation are still unexplored 29